Triazine azo dyes



Patented Feb. 1,

Eduard Bernaseoziig. Basel, Switzerland}- as'signorto. Cilia... Iiimitedfi- Basel, Switzerland, a- Swiss No rawing Application Jnne 80; 1945; Serial, No. 60mm 1n-switzermnq=mgpsv9;1944- aclai s. (omens- 152 It has already been proposed-yto manufacture dyestufis which contain two different lake-forming components, namely, on the onehauda the 7 atomic grouping formed by coupling a diazotized 0rtho-.-amin0phen01 with Z-aminm-fiehydroxynaphthalene-'Z-sulfonic acid in an alkaline medium, and, on the other hand, the radical ofa dyestufi" of ,the' typeof 4ram-ino-4 hydroxy r; -1 azobenzene-3 carboxylic' acid. ThusgU'; 551?. t

ent' No.- 13667312 describes in- Example-1s the ternary condensationproduct from 1' Incl' of. =cyanuric chloride, 1 molof' the azo*-dyestuffrfloln' :diazotized 1-amino 2-hydroxybenzene+fi sulibnicir :acid and 2-amino-5-hydroxynaphthalene-F5111 fonic acid (coupled in an alkalinemedium); I: mol of 4-amino'-4'-hydroxy=1-: 1f "-azobennen'e-B" *carboxylic acidand 1 moliofaniline;v Further; U. S; Patent No. 1',783;084"describes themanufa'm ture of the mixed; urea from 1 mol. o'fi the-am dyestuff from diazotized' 1'-ami no=-2:hyd1:oxy benzene-Becarboxylic acid fi sulfonic'" aci and- (coupled in an alkaline medium)" and 1" m'oPof 4-amino'- 4- hydroxy -1:'1- azobenzene- 3"=car-' boxyliciacidz These-dyestuffs are distinguishedfin'that they,"

yield copper compoundswhichiare'valuabledirect'i dyestuffs. If; on the other hand; the copper compoundsof thesedyestuffs are formed. on the fiber, by .after-coppering textilesdyed 'with the. metal-free dyestuffs, the wet-fastn'e'ss"properties; although improved, do" not meet" present-dayrequirements. I The present-invention is. based on thenbsenva tion, that; in contradistinction. to. the. aboye.

known dyestufis, the new products which. cofferspond in the free, form to the general formula.

d-m-m.

in which R$1-, Rz and R3 represent unsulfonatedv 45 benzene nuclei of" which R1 carriesa hydroxyl group in ortho-p'osition tothe azo linkaige contains theNH-groupandthe" axe -linkage; contains the' Nfl group' and the azo linkage' -in 2i contains: a). hydroxyl group -in 4pesitionwith resbect? to the acelinkage and a carboawl' g'roup in! owl'imposition with respect athe sm hy: drmcyl' group, and R represents also an smfonated benzene nucleus 01- stands for a radi cali'=Rl1 ,-N'*-N +Rb i-n=which-R5and rte 'repres ent unsulfonatedt benzene nuclei;- Rs containing the? Nmgreun and the: a2o-linkage m l z4 positibn relativelytc oneanother, and containing a:

hydroxyl group in 4-p osition with respect totlrfe sw-linna eand a} carbonyl group ortho position with. respect to the; saidmydlo'xyP group; amdye'sflufis whose e'epp'en compounds, when nmducem on. the. fibe yield: dyeinesj having; ex- 1' cellentfastness? to: lightand wet; fastnessi propextiesz.

Among these dyestuffs those+ariee nanticularly valuable wherein R4 represents anunsulfcnated benzene radical.

But also the; dyastufis corresponding to the free. form to. the. g neral. fcrmula.

benaenw nuclei: in; which; Bin contains; a hydroxyl gnoumin; onthoenositiomwith" respect.- to; the azbgmum-Bz and: R4 contain the; N Hag-mun: and? the azoelinkagez im 1?: QETPQSifiOIT: relatiyelwto one: an- 013 1813 .an R3 and: contain; as. hydmxyl: group in 4-positiom'with"respeccto: thegazcelinlage and a. carboxylgroup in. QI'iihOrQOSitiQIl, with. respect tb;;t1iishydroxyl; ioup; constitute. Valuable pxcdiucts;

The. manufacture of. the. new. d e tuffs. can. be. deduced from" their composition.

For example, they can be obtained by causing 1 molof a'- diazoti'zed orthc-aminophenol free: rrrannsul rbniw acid groups, 1" mm of 2 aminQ F-hyd'roKynaplithalene 7 sulfbfiidiacid 1 mal of cyaniirivchl'oride on 1" moi of cyanu'ric bromide: and 1 -2 men of 4'-amiho"-4'- -hydi'oxy= lcl -azobenzene' 3- ca'rboxylic acids free mmsulfb'ni'c acid groups to"re'act with one anotherin such a mar-men that the diazo ccr'npound 1 :4-9osit-ion -relatively to onc another: and R2, 50 couples in the c-position of the amino hydroxy naphthalene-sulfonic acid, that one halogen atom of the cyamuic halide reacts with the amino group of the amino-hydroxynaphthalene sulfonic acid, and that 1 to 2 halogen atoms of the cyanuric halide react with the amino group of the amino-hydroxyazobenzene carboxylic acid, and causing the halogen atom which may not have been converted to react with a primary aromatic amine of the benzene series which is free from sulfonic acid groups.

The products can also be obtained by using for the condensation, instead of one or both of --the amino-hydroxyazobenzene carboxylic acids, an amine or amines of the benzene series which contain in 4-position to the amino-group a second amino-group or a group convertible into an amino group, condensing the product, and then, after the reaction and, if required, after converting into an amino group the group so convertible,

diazotizing or tetrazotizing the condensation product and coupling the resulting diazo compound with 1 mol of a hydroxy-compound of the benzene series carrying a carboxyl group in orthoposition to the OH-group and capable of coupling with diazo-compounds in 4-position with respect to the hydroxyl group, or coupling the resulting tetrazo-compound with 2 mols of such hydroxycompounds which may be the same or different. It is selfevident that the order of succession in which the aboveoperations are performed should be so chosen that the reactions will take the desired course. By observing this precaution reaction of the diazotized condensation products with the. aminonaphthol sulfonic acid residue is avoided.

For the introduction of the radical R1 into the new azo-dyestufis, there may be used, for example, the diaz'o compounds of thefollowing amines:

l-amino-2hydroxybenzene, l-amino-Z-hydroxy- 5-chlorobenzene, 1-amino-2-hydroxy-5-n.itr0- benzene, 1-amino-2-hydroxybenzene-5-sulfamide, and the like.

For introducing the radical -N I-I--RzN=NRa the following aminoazo-dyestufis may be used:

For the purpose of introducing the radical --NHR4"there can be used, besides the already indicated aminoazo-dyestuffs, simple amines, such as aniline, 1-aminobenzene-3-carboxylic acid, '4-

aminoacetanilide, etc.

,The introduction of one or both of the emodyestufi radicals can also be eifected by causin 1 to 2 hologen atoms of the cyanuric halideto react with compounds such as 1-amino-4-nitro-,

benzene, l amino 4 acetylaminobenzene, 1- amino-2-methylor 2-methoxy-4-nitrobenzene, 1eamino-Z-methoxy-5-methyl 4 nitrobenzene, etc. The nitroor acylamino-group is than converted in known mannerinto a primary amino group which is diazotized and the diazo compound is coupled with hydroxy-carboxylic acids of the benzene series, such as l-hydroxybenzene- Z-carboxylic acid or 1-hydr0xy-5- or -6-methy1- benzene-Z-carboxylic acid.

The new dyestuifs are distinguished by their affinity for cellulose fibers, either of regenerated or natural cellulose. They can, therefore, be used for dyeing cotton, ramie, jute, viscose or cuprammonium artificial silk, staple fibers of regenerated cellulose which may, if desired, be matted with titanium oxide and which may be produced either by the viscose or cuprammonium process. The dyestuffs can also be used for dye,- ing mixtures of these materials with, for example,

animal fibers such as wool or silk. The new dyestuffs dye these materials more or less reddish orange-brown shades which become darker by after-treatment on the fiber with agents yielding copper, for example, copper sulfate or an alkaline lent wet fastness properties, combined with a very good fastness to light.

Dyestuffs having similar properties are also the wherein R1, R and R3 have the above indicated significance. The manufacture of these dyestufis can also be deduced from their composition.

Such dyestufis can be obtained, for example, by causing 1 mol of a diazotized orthoaminophenol free from sulionic acid groups, 1 mol of the 2 amino 5 hydroxynaphthalene 7 sulfonic acid, 1 mol of phosgene and 1 mol of a 4 amino 4 hydroxy 1:1 azobenzene 3'- carboxylic acid free from sulionic acid groups to react with one another in such a manner that the diazo compound enters into the fi-position of the aminohydroxynaphthalene-sulfonic acid, and that thephosgene reacts with the amino groups of the amino h'ydroxy-naphthalene-sulfonic acid and the amino'azobenzenecarboxylic acid in such a manner that a urea derivative is formed. It

is also possible, for'example, to produce in known:

Example 1 18.8 parts of 1-amino-2-hydroxybenzene-5- sulfamide are dissolved in parts of water of 50'C. and 25 parts of hydrochloric acid of 30 per cent. strength. The solution is cooled to 0 C. and diazotized with 6.9 parts of sodium nitrite in 25parts of water. In the meantime 66.4 parts or" the ternary condensation product prepared in known manner from one mol each of cyanuric chloride, 2-amino-5-hydroxynaphtha1ene-7-sulionic acid, 4-amino-4'-hydroxy-l:1azobenzene- 3' -carboxylic acid andaniline are dissolved at 50 C.-,in 1600 parts of water and 30 parts of sodium carbonate. The solution is cooled to 10 C. with ice and mixed with the diazonium solution. The mixture is stirred until the diazonium compound cannot be detected any longer. It is then heated mum to 80 C. and the dyestufi which has formed is 1. The diazoniuni solution is poured to a. som salted out. This corresponds in the free form to tion of 82.8 parts of the ternary condensatiom the formula product prepared: in known manner from 1 mol,

After filtering:anddrying thereisfobtained ahdarlc of cyanuric chloride, 1 mol of 2 -amino-5v-hybrown powder which..cotton fromiai-bat droxyna-phtfhalenez-f-suifnict acid andiz'lmo 1 which copper, sul iat'e. and' sodiilmltariiriate i 4;- azmirroie i hydioxazi- 1 '-azO 5enZenei'*- 3? been added, red brown, shades possessing. geodl boxyliir'arcidiandimf gart'sf'otfsodium; carbonate-1m fastne'ssto light andfioiwash'ihg. moopartsyoffwater: Whexrcouplin lisidpmplefig If this example l-amino-Z-liydroxyhenzen thedyestufisworked upfin.kmwmni men; 5-su1famide is replaced byf-amfim-z lixdrogyresulting' i d'yestuflfwhich;conresmrrds;mn'tiieptree S-nitrobenzene or 1-amin0-2-fiYdYOXY?5 -cfi1bibformtbime tornuflaz.

0 con benzenezthererame obtained reddeivdye'stumszhaw 3O cuttnm from aeimthflcontainiirgesaltisi ing the same fastness properties. brown 'shazdes (it? fiiistness Similar dyestuffs are also obtained by replacing washing. I the 4-amino-4-hydroxy-1:1'-azobenzene-3-carboxylic acid by another; similarly constituted V zene fi -sulfamide by: aminoazobenzen'e cartioxylic acid; for example, 35 benzeneor l amino-W hydizoxy 54min the 4 amino-2-methyl-4'-hydroxy-1:1'-az obenthere areobtaiii'ed similar"dwesiluflsihg' f'ttiet zene-3'-canboxylic acid the 4"-amino- 2metfiy1 5- same fatness-properties; methoxy-4'-hydroxy-1:1'-a.zobenzene 3' car- Furthermore, 1 mol or 2 mols of thee-aminoboxylic acid, the 4-amind-3/-methy1-4'-hydroigy- 4-hydroxy 1:1-azobenzene-3'-carbo;;ylic acid 1- :1-. -azobenzene-&f-carboxylic acid, or the: 40 cam-be replaced by 1 mol or 2 mols of. the aminoamino-245 -dimethy1-5 methox3t 4' hgdroxinam-dyestuffs recommended in the introduction 1:1'-azobenzene-3'-carboxy1ic acid, andithe an for introducing the radical line by the paral-toluidine or the. t-amino-salilcylic acid. Such dyestu ffsicorrespondtfor' examh pie, to the formulas I 4 7 on H ii: Obiki I I slomm Hols N-yi I V 1i K A r it i j Example 2 A 18.8 parts of l-amino-Q-hydroxybenzene-S elsiestuifis -rmrespond in the freeform to sulfamide are diazotized as describedinmxamplejhQfMHIaS V 7' i H 'i t coon N=N N/ om N I H0; N- '(5- 0H t i c OH OH 1 0 V s 6 .5 i' 1 V V Q "l y a 00011 N: N/$\N om "doggy 1 m N AVQM OH 1!! N 1k (ton. (20011 I Example 3 As stated in the opening part of the specifi- 100' pafts f cotton are entered at 0500 cation, the dyestufis of the invention may be into a dyebath containing 3000 parts of water, u or dyeing mixed a s, o example, mix- 1.5 parts of the dyestuffi obtained as described tures of W and Viscose staple fiberthis in the'firs't paragraph of m' 1' and 2 parts purpose it is advantageous to conduct the dyeing of anhydrous sodium carbonate. The bath mm in a neutral t in the p e f sodium perature is raised to 90-95 C; in the course'of hr or potassium chromatehour, 30 parts of crystalline sodium sulfate ,What I claim is: are then added, and dyeing is conducted at the 1. An azo-dyestuff of the formula on H V Zm4v=rr-on Q N N I (500B NHaOa HOsS- IIP- /(IJNR same temperature for houn, .There is then 7 wherein R is selected from the group consisting addedto the dyebath a solution of -2 parts of of crystalline copper sulfate and 2.5 parts of tartaric Y 0 acid in 100 parts of water, which solution is Y p003 neutralized with caustic soda solution, and the cotton is treated for hour at about 95 C.,the O and cotton is then rinsed and dried in the usual maner. 'It is dyed fast red-brown tints. 2. The azo-dyestuif of the forrnula COOH OH OH N-N'=N--0H G i N/ HaNOa Hols N-it (]J--N 3. The 'azo-dyestuff of the formula coon ou 7 V =N U N v g OOOH m. m N4 a N=N OH It r t w r EDUARD BERNASCONI. REFERENCES CITED The following references are of record in the V I file of this patent:

UNITED STATES PAEENTS Number Name Date 2,268,919 'Anderau Jan. 6, 1942 2,387,997 Kaiser L Oct. 30', 1945 3,396,659 Kaiser Mar. 19, 1946 Certificate of Correction Patent No. 2,460,618. February 1, 1949.

EDUARD BERNASCONI It is hereby certified that errors appear in the printed specification of the above numbered patent requu'ing correctlon as follows:

h Column 3, line 69, for hologen read halogen; line 74, for the word than read t an;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 14th day of June,- A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

